Manufacture of sulphuric acid



June 16, 1931. H. PETERSEN 1,310,253

MANUFACTURE OF SULPHURIC ACID Filed May 5, 1925 a regular aka? puch/zg' 7 M PtentedJune 16, 1931y untreu- STATES Parana' ori-vica HUGO Parmesan, or BnRL'N- srnenrra GERMANY@ MANUFACTU'RE OF SULPEUBKC .ACIIDy Application med May 5, 1925, serial No.

l have filed applications inGermany,

1925, serial 8130/1925; in Spain, January 17,y

15 1925, serial 15121;

1925, kserial y15316; 1925, serial -333/863; March 26, 1925-; in the Netherlands, (Holland) March 10, .1925, `serial y29592; in the ZSVNetherlands, (Holland) y,December 30, 1924,

serial 28930; in Belgium, December 24, 1924,

serial 256575; in Belgium, March 10, 1925,

serial 257836; in France, March 10, L1925,

serial 819. 1 Y This invention hasreference to the manufacture of sulphuricacidby,means ofy oxides of nitrogen, kand it refers in particular to means ofincreasing the yefficiency, ofthe socalled nitro-sulphonic yand nitrosyl sulphuric 30 acid commonly called nitrous vitriolvvhich is employed as a vehicle for the action of the 'oxides of nitrogenupon the gases of sulphurous acid or of sulphur-dioxide, and itfis one of theimportant objects of this inventionto so increase the reactivityI of .this compound that the formation of sulphuric acid may be 1in Spain, March 31, .in lItaly, April 2, in Czechoslovakia,

chiefly brought about by this compound in-v stead of yby gaseous oxides of nitrogen, as

heretofore generally practised. The increase r ofreactivity or of intensity of the action of the nitro-sulphonic acid according to this invention which may be produced both by the repeated `acton of comparatively strong 1 solutions of this compound upon; the gases of 3* sulphurous acid, aswell as, on the otherhand,

by thegreatly increased, contact ofthe nitrosulphonic acid and ofthe oxidesof nitrogen either produced lby its that practically the use of the usual so-calle'd .duced byv means yof fans,

decomposition ork presentin the reaction chambers, may be suchy 28,126, and infeermany ivramh` 13, 19:23.E

lead-chambers may be entirely dispensed With. In the practice of my invention in View of the f desirability of a very great lincrease, in contact surface and of so conducting thereaction that the gaseous and liquid reagents may rey peatedly acts upon f each othery artificial resistances -of comparatively great, compactness are'employed, together With'a regulation of the strengthof the rinsingliquors and of` the velocity of the gases, preferably by either using ypacking or filling bodies of comparatively very small size, as compared With those heretofore vin use for the llingof there- -actionlchambers or enclosures, or by mounting the ordinary packing bodies or blocks more closely spaced than heretofore,-so that the resistances produced Will have tobefovercome by anincrease of movement, or of velocity of the gases, which eiect may be proexhausters, ventilators or the. like. In further pursuance of my invention I may provide for the gradingof ,the packing or lling of the reaction enclosures in .accordance with the intensity of the reaction, and in kvievv thereof a coarsery packing may be used for denitrating purposes than'for absorption purposes which as a. rule takes place more slowly. My invenconliguration and arrangement of reactionV chambers or otherA enclosures in which the reaction is carried on bythe aid of the packj t ing or filling referred to, such enclosures in one embodiment of my invention being given a broad shape of considerably increased diameter, `so that the gases in .view of the ref sistance oiferedto their passage in they vertical direction'will be compelled to spread laterally and to occupy fthe entire cross sectional area of suchf reaction enclosures. Inasmuch as it is of importance to produce a thorough reaction by the repeated revolving, so to speak, of thereactingmolecules, it will 'sometimes be of `advantage in the practice of my invention to produce the quantities of acid intended forsale or for other outside uses, and constituting the output of thek plant, in separate reaction enclosures, towers or the like, Where ka thorough denitration of the product obtainedbythe revolving action retion further comprises aparticular form and i ferred to may be effected by the fresh sulphurous gases and by water. By acting in this manner highly satisfactory results are obtained with gases of rather low or greatly changing contents of sulphur-dioxide, and it also becomes possible to consume and thoroughly convert into sulphuric acid the last traces of sulphur-dioxid contained in sulphur gases, furnace gases and the like which it was very diiricult to deal with in accordance with the previous methods and operating apparatus. These and other important advantages will appear as the specification proceeds and from an inspection of the drawing.

On the ,accompanying drawing forming part of this specification I have shown by way of exemplification only and diagrammaticallyY a combination y of enclosures, chambers ortowers, or boxes with pac-king or filling means, suitable for the purposes of my invention constituting a sulphuric acid plantprovided with different kinds of packing. In 'accordance with the method of my invention which is based upon the increased or more intensified reactivity of the nitrosulphonic acid and nitrosyl-sulpluiric acid the contents or acid may be so .increased that it will act as a carrier of nitrogen-oxides and thereby become a great oxidizer for the sulphur-dioxid ofthe sulphur-gases. In both cases the eiliciency of the nitrosulphonic acid upon which the so-called lead-chamber process is usually assumed to depend, is vastly increased, and this result may be accomplished or aided to a great extent by the increase of the velocity of the gases and the comparative compactness of the filling or packing of the containers, enclosures or the like.-

As the rinsing acid I may use solutions of nitrosulphonic acid or nitrous vitriol in high grade sulphuric acid, and as an exemplitication this solution may be obtained by dissolving chamber-crystals in high-grade sulphuric acid and under such conditions of temperature and concentration that decomposition of the solution does not take place byV such dissolving action and during the rinsing of the reaction spaces. No denitration is effected during the production of sulphuric acid itself by the use of this solution as an oxidizing agent for the sulphurdioxid,the

reaction and oxidation going on in the liquid itself, which clearly,differentiates this invenf tion from prior proposals in which in mixing concentrations approximating 600 B, were to be usually obtained by an increase of temperature, a fact which is well-known to experts to be one of the best means of denitration. This substantially copious evolution of nitrous gases in the production spaces and the rise of temperature are avoided by proceeding in accordance with my invention.` In my process only that portion of the finished sulphuric acid which is intended to degrs. Be.

the strength of nitrosulphonic go to the market, is denitrated in any well known manner in a special space, and this denitration evidently does not constitute a part of my invention. By preparing the rinsing acid for the acid-production spaces in the manner referred to and using it in said production spaces it has been ascertained that the strength of the acid will then rise to 66 at 150 centigrade with a content of nitrosulphonic acid up to 35%, calculated on nitric acid of 36 degrs. Be. This content under some conditions may even still be further increased.. The denitration of the acid may be effected only for the purpose of producing the acid for the market or for other uses, where low content of or substantial freedom from nitrogen is desired. i

It is one of the important advantages of this method of procedure that sulphuric acid of great strength is obtained which is adapted to more readily absorb nitrous compounds than the usual chamber or tower-acid of to degrees Be. strength. In further pursuance of my invention it has been ascertained that these solutions of nitrosulphonic acid in high-grade sulphuric acid may be made to act repeatedly upon the sulphurous acid gases without any liberation of nitrogen oxides taking place which behavior differs considerably from that of solutions of nitrosulphon'ic acid in weaker grades of sulphuric acid; in these solutions the oxides of nitrogent are immediately rliberated by the reaction with sulphur-dioxid and in consequence thereof can be used only once. With a sulphuric acid plant of ordinary arrangement and employing as an instance hot gases of SO2 and containing about 6 to 7% per volume of sulphur dioxide one may use for instance atoWer or the like into which the fresh gases or only a. portion thereof are caused to enter and which'is rinsed in the usual manner for the production of this marketable acid only which is to be substantially denitrated and concentrated. In the case of larger plants possessing for instance four Glover-towers disposed in parallel, two of such .towers whenever required may be used for this purpose of producing marketable acid.y All the other reaction spaces in the case above referred to are fed with nitrosulphonic acid of such amount and of such strength that the acid discharged Will still contain very great quantities of nitro-sulphonic acid the degree of which must be so adjusted that there will be the least possible liberation of gas in the escaping acid, It has been ascertained in the practical operation kof the process that this prevention of the liberation of gas will already be acccomplished if the disch arged liquid will still contain 0,5% of nitro-sulphonic acid,` as rexpressed in nitric acid of 36 B. However, far more favorable results are obtained with a large-r content of nitro-sulphonic acid in the discharged Nacid, thus fo-r instance withf a content above 2%. The percentage may be so increased as rto amount to about 5/6- of the initial percentage of nitro-sulphonic acid. ln some cases the total vinitial contents of nitro-sulphonic acid remains unchanged and sometimes the percentage thereof` in the escaping acid may even be increased, which is due to the fact that the reaction space, toweroi tlie like has already received-a certain amount of'oX'ides ofV nitrogen from the sulphur gases fed thereto, sc thatit will operate in part as a Gay-Lussac-space. Y i

lnffurtherpursuance of this procedure of "maintaining a supplyof'nitro-sulphonic acid n in the reaction spaces it will be preferable to cause thewentire iiitrosulphonic acid from yGay-Lussac section to .be acted upon by the gases as far as *possiblel at the front portion [of the system withL the'result that the oxides of nitrogen which are liberated in this comparatively hot Gay-Lussac zoner'of the system will be compelled ,to pass through a comparatively long reaction passage and lwill rthereby greatly contribute to the formation of sulphuric acid., l'trhas been ascertained to produceparticularly favorable results in the operation of the process if'gaseous oxides of nitrogen are caused to react upon the sulpliurous acid simultaneously with the oxides of nitrogen contained in the nitro-sulphonic acid. n Y L e YWhen acting `in this manner, it is-easyto overcome the diiiiculties heretofore experienced in thewo-rking up of the last remnants #of SO2 particularly in the case of gases with considerable variation in the contents of SO2. As a general workingv rule of this part of the` process in which'operating acids of very high strength' and consequently with only slight admission ofA water are employed suchk an amount ofl nitro-sulphonic acidli'as been found to produce favorableresults'that its contents of Aoxides of nitrogen calculated 'on v'nitric acid vwill amount to a multiple of' the SQQ' 'entering the system. The proportion ymay be sofincre'ased that the oxides of nitrogen amount to sixA times or more ofthe n amountI of SO2 existing, and as a practical instance a iiitro-sulphonic acid lof 8% and above may beused. y V

V rlhe degree of density of the nitro-sulphonic acid employed may'vary, and for practical purposes a strength of55 to 60k degrs. Be. or even 66 degrs maybeused. As an example of a preferred way 'of arranging the different'y reaction chambers I may' refer to an exemplification of a system of apparatus -comprising as an instance four towers.- Of these the first tower-'would' correspond to kthe ordinary Glover-tower, and it is `rinsed yfrom the third and fourth towers, this latter fourth tower fur'ictioningr as 'a kind of Gray-Lussa'c-,towerv and whichl may be `rinsed with Yacid of '60 degrees Be. or more,

while the third tower receives an acid of, say 55 to Y57 degrees B.` This third tower besides being yutilized for the production of the nitro-sulphonic-solution will also'serve to retain any remnants of S02 which might have passed through the second tower. This second tower inwhich the gas is preferably caused toflow in the downward direction, may be rinsed with sulphuric acid ofrO vdegrees-Be. In this second tower the solid chamber-crystals are formed wliichwill be dissolved iii the strongsulphuricacid.- The formation of these `chamber crystals takes place in vpresence of the limited quantities,

of water introduced from the first tower, and whenever necessary some additional water may be introduced, suiiicient to insure theY formation of these crystals, but insuiiicient to y produce decomposition thereof. Instead of but one tower being used for each stage a plui ralityof towers may be employed in the various stages, nory am I restricted to the particular yconcentration of the acids herein stated by way of exemplitication only. y As an 'exemplificationof means for bringing `about the intimate contact and free distribution ofthe reagents I have shown in the the different chambers which are packed in lll() such a mannerthat comparatively y'considerf able resistances to ythe passage of the gases are created'in the chambers. This object may either be accomplished by using plates or the like m with many perforations or packing blocks 1 which are more closely spaced than usually or the individual packing bodies are given. such a vdegree ofjlineness thatl they present great obstacles to the free passage of 'the gases.y In order to overcome these re-v sistances, an exhauster, fan or the likenot is arranged at any shown inthe drawing, Y suitable point of the system which the gases and at the same time Vproduces. ay whirlingaround and atomizingl ofL the thin film 'or layer of liquid on the surfacejof the packing or of the plates, blocks or the like and imiparts to them andy to the gases in the particular enclosure ay veryviolent movement'in view of the fact that the pressure employed f is considerably vin lexcess* of the pressure re-v quired to overcome the internal resistances of the system.y The filling or packingshould of course consist of perfectly acid-proof materialand the reagents gases and liquids may f be conducted through and in contact with the packing in the same or in ycounter-current direction.

The required very fine distribution of the reagents is further facilitated by.a very high degree of subdivision or granular distribution or coinpactness of the packing or filling bodiesemployed for the production of the artificial resistances. The subdivision of the packing must be considerably below the size of packing or filling bodies heretofore used in reaction towers. As heretofore practised, such packing bodies of regular or irregular shape were of a size to be measured by inches or centimeters, while for the purposes of this invention the size of the packing or filling bodies to be employed should preferably be such that their diameters am'ount to but fractions of an inch or even of one centimeter. In connection therewith it is of advantage to so distribute the packing that those parts of the system of apparatus adapted for the denitration or Glover-section of the plant are filled with somewhat larger pieces of packing as indicated at p in the drawing as compared with those parts serving for the absorption A and for which packing material q of smaller size is used, inasmuch as the denitration takes place at a considerably quicker rate than the absorption. For the packing of those parts of the system intended for the reduction and denitration pieces of about walnut-size (say labout 3 centimeters or about one inch) are preferably employed, while for the filling of the absorption containers the granulation should be as low as l to l0 millimeters (0.04: toi 0.4 inches). Both these kinds of granulation, including the walnut size, differ very considerably from the sizes of granulation heretofore employed in connection with reaction towers. The packing or filling may be placed on a bedding or foundation of blocks, plates or other bodies z', c, so asto allow of the admission of gases and of the discharge of liquid. y

In view of the ineness of granulation of the packing the cross-sectional sizes and heights of the reaction spaces heretofore employed may be changed, in order to avoid producing too high resistances which might interfere with the movement of the gases. The height of the containers according to my invention may therefore be less and the diam. eter may be larger than heretofore, and in accordance with the quantities of gases to be handled and in view of the fine granulation of thematerial of the packing, the ratio of the' dimensions may be such that the diameter is greater than the height. y

Insome cases, it may be advisable to employ resistance bodies or packing presenting less obstructions than in the form of execution above mentioned, and a somewhat coarser granulation than has been mentioned with reference to the packing material referred to;

vthe sulphurous acid gases into sulphuric acid, the'packing may also be employed with advantage in connection with working acids ycontaining smaller percentages of nitro-sulphonic acid, such acids running all the wayl from approximately 54 to 60 B. and adapt ed to be denitrated in the usual manner. This strength of acid is equally well adapted to absorb nitric oxides when submitted to the action of the artificial resistances according to this invention.

In further pursuance of this part of my invention, it has been found to be of advantage to use such acids particularly at the entering and the exit portions of the system of apparatus. f

The reaction produced in this manner may be further assisted by arranging a reaction chamber filled with any kind of packing or lillingmaterial and in any desired manner between the denitriication and absorption portions of the plant, and in such intermediate reaction chamber the formation of sulphuric acid is to take place substantially by the action of gaseous nitrogen oxides upon the sulphurous acid. This intermediate chamber which, if desired, may be composed of several sections is keither rinsed or not rinsed. In case of its being rinsed, this may be done with acid of different strength or even with water. A sulphuric acid of 63 B. strength which may be produced in the operation ofthe plant itself, has likewise proved to be suitable for the purpose. It has been found to be of great advantage to cause the gases to pass through this reaction space in the downward direction: with this kind of flow of gases theyare compelled to become distributed over the entire sectional area of the container. This intermediate reaction space does not require such small-sized filling or packing bodies or so finely comminuted packing material as the principal parts of the system above referred to, or any such close setting of blocks or plates as would-create appreciable resistance, as required for those principal parts of the system.

In accordance with my invention I am also enabled to avoid the necessity of using unduly large amounts of lead, as required by some of the processes heretofore suggested for the production of sulphuric acid by means of oxides of nitrogen, but without the usual lead chambers, the cost of the lead for the small lead containers used in some of these with local and other requirements and Withacid-proof finely divided distributing material, comprising granular packing bodies having individual grains ranging from about four-tenths of an inch diameter to about one f inch diameter, and under such conditions, as to substantially prevent denitration of the liquorduring the treatment, thereby'oxidiz-` ing the sulphur-dioxid into sulphuric acid, substantially maintaining at least the original percentage of nitrosulphonic acid in the resultinc'lmixed acid liquor, withdrawing a certain portion of said liquor and denitrating` said portion.

' HUGO PETERSEN.

out deviating from the scope and spirit of the invention, as defined in the appended claims.

l. In the manufacture of sulphuric-acid by the chamber method, treating sulphur-dioxid gases with strongsulphuric acid liquors containing nitrogen oxidsx and in presence of oxygen, absorbing the gases in the liquid in the presence of iinely granular packing bodies, substantiallyv not exceeding fourtenths inches in diameter, denitrating a certain portion of the liquid produced in the presence of granular packing bodies, substaiitially not exceeding one inchindiameter, and producinga vigorous movement of the gases of reaction. v

A 2. In the manufacture of sulphuric acid by the chamber method treating sulphurdioxid gases lWith strong sulphuric acid liquors containing nitrogen oxids and lin presence of oxygen,-denitrating a portion of the liquor produced in thefpres'ence of'granular packing bodies, substantially not exceeding individually one inch in diameter, absorbing the gases produced by themaction ofy y sulphur-dioxid in sulphuric-acid-liquor in v ther presence of granular Y, packing bodies,

i tially not exceeding four-tenths of an inch Ysubstantially not exceeding four-tenthsof an L inch each in diameter, and passing thev gases between the denitrating and absorbing stages in presence of packing bodies of a size exceeding one inch in diameter.

3. In an apparatus for the manufacture of i sulphuric acid bythe chamber method they combination With a `plurality of relativelyk broad inter-commu'nicatingl reaction chambers, and gas-admitting and liquid-admitting Y means on said chambers,

bodies of substantially one inch size inl certain of 'said chambers adapted for deni'tration, and granular packing bodies, 'substansize in others ofl said chambers, adapted for absorption purposes. i

4. The manufacture of-sulphuric acid by the chamber method, Which consists in treating sulphur-dioxid-gases With strong nitrosulphonic-acidliquor of ka strength ranging inl density from` about ifty-ve to about sixty-sixdegrees Beaum in the presence of of granularpacking 

